Devices and process for high-pressure magic angle spinning nuclear magnetic resonance

ABSTRACT

A high-pressure magic angle spinning (MAS) rotor is detailed that includes a high-pressure sample cell that maintains high pressures exceeding 150 bar. The sample cell design minimizes pressure losses due to penetration over an extended period of time.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Provisional Application No.61/422,599 entitled “System and Process for High Pressure Magic AngleSpinning Nuclear Magnetic Resonance”, filed 13 Dec., 2010, incorporatedin its entirety herein.

STATEMENT REGARDING RIGHTS TO INVENTION MADE UNDER FEDERALLY-SPONSOREDRESEARCH AND DEVELOPMENT

This invention was made with Government support under ContractDE-AC05-76RLO1830 awarded by the U.S. Department of Energy. TheGovernment has certain rights in the invention.

FIELD OF THE INVENTION

The present invention relates generally to magic angle spinning (MAS)spectroscopy and magnetic resonance imaging. More particularly, thepresent invention relates to a high-pressure magic angle spinning rotorand process for high-pressure magic angle spinning nuclear magneticresonance spectroscopy and imaging.

BACKGROUND OF THE INVENTION

Nuclear Magnetic Resonance (NMR) spectroscopy and imaging are powerfultools for obtaining detailed molecular structure and dynamicsinformation for samples under investigation. NMR methods addressnumerous chemical, physical, and biological problems across variousscientific disciplines. Magic Angle Spinning (MAS) is one of the mostwidespread NMR methods and is the only technique that allows a highresolution NMR spectrum to be acquired on solids, semi-solids, andmixtures of various sample materials. In MAS NMR, a sample is spun at asample spinning rate of several kHz or more about an axis inclined at anangle of 54.74 degrees (°) with respect to the main magnetic field.Sample spinning speeds are used to average out line-broadening effectsarising from common shielding interactions including, e.g., chemicalshift anisotropic-gradients, dipolar-gradients, andmagnetic-susceptibility gradients to give high-resolution NMR spectra.However, despite its wide spread application, MAS has not yet beenreported in the literature at high-pressure conditions exceeding 70 bardue to various technical challenges that remain to be addressed. First,sample carriers cannot be made of metals due to strong eddy currentsassociated with a spinning metal in a strong magnetic field. This leavesnon-metals for sample carriers including glasses, ceramics, and polymerplastics. Early development efforts in high-pressure MAS NMRinvestigated segmental motion of polymers (i.e., interchain distanceswithin polymers) that were plasticized by dense gases. The samplecarrier was a glass tube insert in which gas was cryogenicallytransferred into the carrier using a standard volumetric absorptionmethod. The carrier was then flame-sealed or epoxy-sealed andsubsequently inserted into a MAS rotor and balanced with KBr powder. Thecarrier was pressurized with xenon (Xe) and CO₂ gases. However, (i)reactions under a constant pressure were not obtained, (ii) maximumupper pressure was limited due to the use of thin glass tubes, and (iii)the carrier could not be re-opened to recharge and continue the samplereactions. A later carrier insert was made of DELRIN™ polymer thatincluded an internal seal. The DELRIN™ insert included a cylindricaldesign that was inserted into a ceramic MAS rotor after pressurization.A 94.2 MHz ¹⁹F MAS spectrum of CH₃F gas was acquired using this carrierinsert. However, significant penetration by the CH₃F molecules into theDELRIN™ polymer material was observed over time, with a correspondingreduction in pressure. Similar penetration problems have been reportedin the literature with CO₂ and N₂O gases using MAS inserts made from thepolymer PEEK®. In these experiments, pressure was limited because a fastsample spinning of several kHz or more was required. The sample rotorrequired a small diameter, which complicated the sealing necessary toattain high-pressures with this design. Polymer inserts made of polymerssuch as DELRIN™ and PEEK® are commonly plagued by strong unwanted carbonand/or proton background signals which can mask desired NMR signals insystems containing carbon, protons, or both. Thus, a high-pressure rotoris needed that provides sealing at high reaction temperatures andpressures, minimizes penetrations by sample molecules and fluids at highreaction temperatures and pressures, and minimizes background signalsthat complicate the desired signal, permitting high-resolution NMRspectra and images to be generated. The present invention meets theseneeds by addressing various problems known in the art. Additionaladvantages and novel features of the present invention will be set forthas follows and will be readily apparent from the descriptions anddemonstrations set forth herein. Accordingly, the following descriptionsof the present invention should be seen as illustrative of the inventionand not as limiting in any way.

SUMMARY OF THE INVENTION

The present invention includes a high-pressure (HP) Magic Angle Spinning(MAS) rotor (HP-MAS-R) for generating high-resolution NMR spectra andimages. The HP-MAS rotor of the invention includes a high-pressure rotorsleeve. The rotor sleeve is reusable, overcoming technical problemsassociated with prior art designs. In various embodiments, the samplerotor sleeve (cylinder) is composed of a ceramic. In some embodiments,the rotor sleeve is composed of a zirconia ceramic. In some embodiments,the rotor sleeve is composed of a silicon nitride (SiN) ceramic. Thehigh-pressure rotor sleeve defines an integrated high-pressure samplecell. The sample cell spans the entire inner diameter of the rotorsleeve.

In some embodiments, the high-pressure rotor sleeve has an outerdiameter dimension that ranges from about 4 mm to about 25 mm.

In some embodiments, the high-pressure rotor is a 9.5-mm MAS rotor thatincludes a high-pressure sample cell with a cell volume of at leastabout 350 uL.

In various embodiments, the sample cell includes various lengthsproviding variable sample volumes. The sample cell maintains a selectedhigh pressure with the rotor when sealed.

In various embodiments, the rotor sleeve includes at least one groovedsurface along the inner wall of the rotor sleeve positioned adjacent thesample, cell. In some embodiments, a grooved surface is positioned aboveand below the sample cell along the length of the inner wall of therotor sleeve. In some embodiments, the grooves are micro-grooves. In apreferred embodiment, at least one threaded sealing member is securedadjacent grooves along the inner wall of the rotor sleeve with ahigh-pressure adhesive. The adhesive is preferably applied such that itfills the gap between the grooves and the sealing member, yielding ahigh-pressure seal within the sample cell. In some embodiments, thesealing member is a threaded bushing composed of a high performancepolymer plastic. Polymer plastics include, but are not limited to, e.g.,polyether ether ketone polymer plastics, polyimide polymer plastics,polyimide-imide polymer plastics, including combinations of thesevarious polymer plastics. In some embodiments, a sealing member ispositioned above and below the sample cell, defining the upper and lowerboundaries of the sample cell. In some embodiments, a high-pressurevalve adapter and a sealing valve positioned above the sealing memberprovide sealing within the sample cell. In some embodiments, the valveadapter includes an introduction end that threads into a threadedbushing positioned at one end of the rotor sleeve. The valve adapterfurther includes a conical receiving surface that receives theintroduction end of the sealing valve. In combination, these componentsseal the high pressure sample cell within the high pressure rotorsleeve. In preferred embodiments, the rotor sleeve defining the samplecell does not include a sample chamber insert or a sample cell insert.In some embodiments, the rotor sleeve includes a single opening at oneend for introducing various sealing members including a threaded bushingthat defines an upper or lower boundary of the sample cell. In someembodiments, the bushing is positioned adjacent grooves located alongthe inner wall at one end of the rotor sleeve. In some embodiments, asealing valve introduced into the bushing seals the high pressure samplecell within the high pressure rotor sleeve.

In some embodiments, the rotor sleeve includes a single opening at oneend that includes grooves for threading a sealing valve. The sealingvalve when introduced defines an upper boundary of the sample cell andseals the sample cell within the high pressure rotor. In someembodiments, the sealing valve includes a driving tip head that allowsrotation of the rotor from the driving tip head.

In some embodiments, the rotor sleeve includes a single opening at oneend that includes a grooved surface along the inner wall for introducinga single sealing member therein. In some embodiments, the sealing memberis a threaded bushing that is positioned adjacent the grooves within therotor sleeve. The rotor further includes a sealing valve that whenintroduced into the bushing in the rotor sleeve defines an upperboundary of the sample cell that seals the sample cell within the rotorsleeve. In some embodiments, the sealing valve includes a driving tiphead for rotating the rotor. In some embodiments, the high-pressurerotor includes a spinning tip composed of a homopolymer ofchlorotrifluoroethylene.

In some embodiments, the sample cell includes a pressure greater than orequal to about 1 bar (1 bar=10⁵ Pa=14.5 psi). In some embodiments, thesample cell includes a pressure between about 1 bar and about 70 bar. Insome embodiments, the sample cell includes a pressure between about 40bar and about 70 bar. In some embodiments, the sample cell includes apressure greater than about 70 bar. In some embodiments, the sample cellincludes a pressure greater than about 150 bar.

In some embodiments, the high-pressure MAS rotor allows a samplespinning rate greater than about 1 Hz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate between about 1 Hzand about 100 Hz. In some embodiments, the high-pressure MAS rotorallows a sample spinning rate between about 100 Hz and about 1 kHz. Insome embodiments, the high-pressure MAS rotor allows a sample spinningrate between about 1 kHz and about 3.5 kHz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate up to about 3.5kHz. In some embodiments, the high-pressure MAS rotor allows a samplespinning rate greater than about 3.5 kHz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate between about 3.5kHz and about 5 kHz. In some embodiments, the high-pressure MAS rotorallows a sample spinning rate between about 5 kHz and about 18 kHz. Insome embodiments, the high-pressure MAS rotor allows a sample spinningrate up to about 18 kHz.

In some embodiments, the high-pressure MAS NMR system includes an RFcoil of a double saddle coil design that delivers a localized B₁ field.In one embodiment, the RF coil includes four (4) coil turns. In variousembodiments, the number of coil turns is variable. In some embodiments,the RF coil includes RF shields positioned at respective ends of the RFcoil that minimize background signals arising from sealing componentspositioned at respective ends of the high pressure rotor sleeve. In someembodiments, the RF coil of the high-pressure rotor employs a ¹H Lamorfrequency greater than about 1 GHz. In some embodiments, the RF coil ofthe high-pressure sample rotor employs a ¹H Lamor frequency of fromabout 85 MHz to about 1 GHz. In some embodiments, the RF coil of thehigh-pressure sample rotor employs a ¹H Lamor frequency of from about 85MHz to about 900 MHz. In some embodiments, the RF coil employs amagnetic field strength of at least about 2.0 Tesla. In variousembodiments, the localized RF coil minimizes ¹³C and ¹H backgroundsignals arising from the high-pressure rotor in the MAS NMRspectrometer.

The invention also includes a high-pressure rotor loading/reactionchamber (HP-RLRC). The HP-RLRC includes a holding member (seat) thatholds the high-pressure rotor static while the high pressure sample cellwithin the rotor sleeve is filled with a sample at high pressure. TheHP-RLRC also includes a rotation member that engages and rotates asealing valve of the high-pressure sample cell, which seals or opens thehigh pressure sample cell in-situ while the high-pressure rotor remainsstatically positioned in the device. In some embodiments, the rotationmember is a high-pressure thrust bearing. In some embodiments, HP-RLRCincludes at least one fluid port for introducing one or more fluidsindependently into the sample cell within the high pressure rotorin-situ. The HP-RLRC permits the high-pressure valve of thehigh-pressure sample cell to be turned for sealing or opening the samplecell in-situ at high pressures and reaction temperatures. Thisconfiguration permits contents or reagents to be removed or added to thesample cell in-situ, allowing reactions within the HP sample cell to besustained indefinitely under controlled high-pressure and temperatureconditions in the HP-RLRC. In some embodiments, the loading/reactionchamber includes a thrust bearing that permits rotation of the highpressure sealing valve while the sample cell of the high pressure rotoris under fluid pressures between about 1 bar and 400 bar. The HP-RLRC isitself a high-pressure reaction device equipped with temperaturemeasuring and controlling devices (e.g., thermocouples) and one or moreviewing windows for viewing turning of the thrust bearing and engagementwith the high pressure sealing valve therein. With these combinedcapabilities, a pressure exceeding 150 bar may be achieved with anabsence of problems observed in prior art designs including, e.g., fluidpenetration and loss of pressure. In some embodiments, in situ NMR iscarried out by sealing the High Pressure MAS rotor (HP-MAS-R) under highpressure in the high-pressure rotor loading/reaction chamber (HP-RLRC)and then removing the HP MAS rotor for transfer and measurement in a NMRprobe and repeatedly returning the MAS rotor (e.g., after NMR data arecollected in the NMR spectrometer) to the HP-RLRC and replacingreactants or other constituents as needed. In situ NMR thus provides asnap-shot of reactions occurring at the same pressure and temperatureconditions as those in the HP-RLRC. This capability has not beenpreviously available in the art.

The present invention also includes a method for sealing a sample withinthe sample cell of the high-pressure (HP) MAS rotor. In variousembodiments, the method includes introducing a quantity of a sample intothe high-pressure sample cell within the high-pressure rotor sleeve, andsealing the sample within the high-pressure sample cell at a selectedhigh pressure. The high-pressure sample cell spans the entire innerdiameter of the rotor sleeve of the high-pressure rotor. In someembodiments, sealing the high-pressure sample cell includes sealing witha high-pressure sealing valve. In some embodiments, sealing includesturning the high-pressure sealing valve in concert with a high-pressurethrust bearing. In some embodiments, the sample cell is defined betweena first and a second threaded bushing positioned within the rotor sleeveof the high-pressure MAS rotor. In some embodiments, a valve-adaptercomponent is threaded into position atop the second bushing. In someembodiments, an end plug component is seated beneath the first bushingand a spin tip is positioned beneath the end plug component at thespinning end of the rotor sleeve. In some embodiments, a sealing valveis threaded into position atop the valve-adapter within the rotorsleeve. In some embodiments, the sample cell is sealed prior topressurizing in the high-pressure rotor loading/reaction chamber(HP-RLRC). In some embodiments, the sample cell remains unsealed priorto pressurizing in the high-pressure rotor loading/reaction chamber(HP-RLRC).

In some embodiments, the fully assembled MAS rotor is mounted into abase block portion of the HP loading/reaction chamber device. A topblock portion of the HP loading/reaction chamber device is mountedenclosing the HP MAS rotor within the HP loading/reaction chamberdevice. The mounting of the top block portion includes inserting arotation shaft component through a center channel of the top blockportion to align and engage it with the head of the valve component ofthe MAS rotor sleeve. A screw cap can then be mounted to seal the HPloading/reaction chamber device. Upon assembly, one or morehigh-pressure fluids can be introduced into the HP loading/reactionchamber device at a preselected pressure with a syringe pump assembly orother injection means to load the sample cell of the high-pressurerotor. If unsealed, the rotation shaft is turned to seal thehigh-pressure fluid inside the HP sample cell inside the HP MAS rotorsleeve. In various embodiments, the method further includes analyzingthe sample present within the sample cell at the selected high pressurefor a selected time by introducing the high-pressure rotor containingthe sample into an NMR probe. In various embodiments, the method furtherincludes opening the sealing valve of the high-pressure sample cellwithin the high-pressure rotor to recharge sample or fluid contents orreactants within the sample cell in-situ. In various embodiments, themethod includes sealing the high-pressure sample cell at a high pressuregreater than 1 bar.

The invention also includes a high-pressure spinning method. The methodincludes the step of spinning a sample at a magic angle within ahigh-pressure sample cell at a high pressure greater than 1 bar for apreselected time. In various embodiments, the high-pressure sample cellspans the inner diameter of a high-pressure rotor sleeve of ahigh-pressure rotor maintaining a selected high pressure therein whensealed. In some embodiments, the pressure within the high-pressuresample cell is between about 1 bar and about 70 bar. In someembodiments, the pressure within the high-pressure sample cell isgreater than about 70 bar. In some embodiments, the pressure within thehigh-pressure sample cell is greater than about 150 bar.

In some embodiments, the high-pressure MAS rotor allows a samplespinning rate greater than about 1 Hz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate between about 1 Hzand about 100 Hz. In some embodiments, the high-pressure MAS rotorallows a sample spinning rate between about 100 Hz and about 1 kHz. Insome embodiments, the high-pressure MAS rotor allows a sample spinningrate between about 1 kHz and about 3.5 kHz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate up to about 3.5kHz. In some embodiments, the high-pressure MAS rotor allows a samplespinning rate greater than about 3.5 kHz. In some embodiments, thehigh-pressure MAS rotor allows a sample spinning rate between about 3.5kHz and about 5 kHz. In some embodiments, the high-pressure MAS rotorallows a sample spinning rate between about 5 kHz and about 18 kHz. Insome embodiments, the high-pressure MAS rotor allows a sample spinningrate up to about 18 kHz.

The purpose of the foregoing abstract is to enable the United StatesPatent and Trademark Office and the public generally, especially thescientists, engineers, and practitioners in the art who are not familiarwith patent or legal terms or phraseology, to determine quickly from acursory inspection the nature and essence of the technical disclosure ofthe application. The abstract is neither intended to define theinvention of the application, which is measured by the claims, nor is itintended to be limiting as to the scope of the invention in any way.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 a-1 d show different views of one embodiment of the invention.

FIGS. 2 a-2 c show different views of another embodiment of theinvention.

FIGS. 3 a-3 d show different views of yet other embodiments of theinvention.

FIGS. 4 a-4 e show different views of a high-pressure loading/reactionchamber, according to another embodiment of the invention.

FIGS. 5 a-5 b show an RF Coil of a Saddle Coil design that provideslocalized B₁ fields, according to different embodiments of theinvention.

FIGS. 6 a-6 b show background signal data for an embodiment of theinvention.

FIGS. 7 a-7 b present ¹³C SP-MAS peak intensity data for measurement ofCO₂ as a function of holding time acquired in situ with one embodimentof the invention.

FIG. 8 presents ¹³C SP-MAS NMR spectra for reaction of forsterite powderas a function of time acquired in situ with one embodiment of theinvention.

FIG. 9 presents ¹³C MAS NMR spectra for reaction of forsterite powderacquired ex situ with one embodiment of the invention.

DETAILED DESCRIPTION

A high-pressure magic angle spinning (MAS) NMR system and process aredescribed that overcome various problems associated with conventionalMAS instrument designs. The invention includes a high-pressure MAS rotor(HP-MAS-R) (FIGS. 1 and 2) that maintains high-pressures in ahigh-pressure sample cell in a MAS experiment. The sample cell maintainsa high pressure with a minimum penetration loss over an extended period.The term “high pressure” means a pressure of at least 1 bar. The term“minimum penetration loss” means a pressure loss by penetration of lessthan about 20 percent (%) over a period of at least about 72 hours. Theterm “fluid” as used herein means a sample phase at conditionsincluding, but not limited to, e.g., gas, liquid, near-critical, orsupercritical conditions including combinations of these various phases.In some embodiments, the pressure within the high-pressure sample cellis between about 1 bar and about 70 bar. In some embodiments, thepressure within the high-pressure sample cell is greater than about 70bar. In some embodiments, the pressure within the high-pressure samplecell is greater than about 150 bar.

The invention further includes a high-pressure loading and reactionchamber (HP-RLRC) (FIG. 3) capable of in-situ sealing and re-opening ofthe high-pressure sample cell within the high-pressure MAS rotor. TheHP-RLRC provides sample access at selected high reaction pressuresenabling continued reaction, analysis, or re-analysis described furtherherein.

The invention further includes a localized RF coil (FIG. 4) for use in ahigh-pressure MAS spectrometer that minimizes ¹³C and ¹H backgroundsignals, yielding “clean” high-pressure NMR spectra suitable forhigh-pressure analyses and applications described further herein.

High-Pressure MAS Rotor

FIG. 1 a shows a high-pressure MAS rotor 20, of a pencil-type design,according to one embodiment of the invention. The rotor has an outerdiameter (O.D.) of 9.5 mm, but construction is not limited thereto. Inthe instant embodiment, rotor 20 includes an active sample volume ofabout 350 μL. Volumes are not limited. FIG. 1 b is an exploded viewshowing the various components of high-pressure MAS rotor 20. In thefigure, rotor 20 includes a rotor sleeve (cylinder)₁, a drive (spin) tip2, bushings 4 and 5, a valve adapter 6, an end plug 7, and a highpressure sealing valve (end cap)₈. In a preferred embodiment, rotorsleeve 1 is composed of a ceramic including, e.g., zirconia (ZrO₂),zirconia variants comprising, e.g., Al₂O₃, MgO, CaO, and Y₂O₃, oranother pressure durable material. In various embodiments, drive tip 2is constructed of a machinable plastic (e.g., KEL-F®, 3M Company, St.Paul, Minn., USA) composed, e.g., of chlorotrifluoroethylene or anothersuitable plastic. In some embodiments, bushings 4 and 5 are of acylindrical design constructed of a machinable plastic. Machinableplastics include, but are not limited to, e.g., polyether ether ketonepolymers (e.g., PEEK®, Victrex USA, Inc., West Conshohocken, Pa., USA),polyimide-based polymers (e.g., VESPEL®, Dupont, Wilmington, Del., USA),polyamide-imide polymers (e.g., TORLON®, Solvay Advanced Polymers,L.L.C., Alpharetta, Ga., USA), or other suitable machinable plastics. Invarious embodiments, bushings 4 include threads on both the exterior andinterior surfaces that allow the bushings to be positioned at variouslocations within rotor sleeve 1, e.g., in concert with other threaded(grooved) or assembly components. Location of sealing components (e.g.,bushings, valves, valve adaptors, O-rings) is not intended to belimited. Sealing components can further include materials that increasethe sealing strength for high pressure applications including, but notlimited to, e.g., metal oxides, graphite, and polytetrafluoroethylene(PTFE), including combinations of these various materials. All sealingmaterials as will be implemented by those of ordinary skill in the artin view of this disclosure are within the scope of the invention. Nolimitations are intended. In some embodiments, valve adapter 6 has athreaded end portion that inserts into, and screws along, the interiorreceiving surface of bushing 5. High pressure sealing valve 8 includes ahead portion, and a tapered end portion, that screws into the receivingend of valve adapter 6. In some embodiments, end plug 7 is positioned onan opposite side of rotor 1 and includes a threaded end that screwsthrough the interior threaded surface below bushing 4. In the instantembodiment, drive tip 2 inserts into the bottom of rotor sleeve 1,providing rapid set-up for spinning a sample, and easy replacement ofcomponents of rotor 1 when needed. FIG. 1 c is a cross-sectional viewshowing the fit of the various components of rotor 20, in assembledform. In some embodiments, grooves 14 are machined in rotor sleeve 1 atselected positions along the internal surface at respective ends.Grooves 14 are introduced, e.g., using a diamond mill that creates arough surface. In the instant embodiment, grooves have a preferred depthof about 127 μm; distance between two adjacent grooves is about 793.75μm, but groove depth and distance between grooves are not intended to belimited thereto. Bushings 4 and 5 insert into, and screw through alonggrooves 14 positioned along the milled surface of rotor sleeve 1.Bushings 4 and 5 are secured in place adjacent the threaded surface,e.g., at respective ends of MAS rotor sleeve 1, in concert with ahigh-pressure adhesive including, e.g., an Aremco-Bond™ epoxy adhesive(e.g., adhesive nos. 631, 526N, and 526NALOX2310) available commercially(e.g., Aremco Products, Inc., Valley Cottage, N.Y., USA), which isallowed to cure.

Bushings 4 and 5 form high-pressure seals within rotor sleeve 1 inconcert with O-rings 9 positioned above and below bushings 4 and 5 inrotor sleeve 1. In a preferred embodiment, O-rings 9 are composed offluoroelastomers (e.g., VITON®, Dupont Performance Elastomers, LLC,Wilmington, Del., USA), but polymers selected for use are not intendedto be limited. For example, in other embodiments, O-rings 9 are composedof a nitrile-containing elastomer (e.g., BUNA-90®, WARCO BILTRITE,Orange, Calif., USA), or another suitable elastomer. In the instantembodiment, O-rings 9 have an exemplary dimension of 7×1.5 mmO.D.×cross-section (CS), but are not limited thereto. The threaded endof valve adapter 6 screws into the interior receiving surface of bushing5. Bushings 4 and 5 define a sample cell 3. The present embodimentprovides a sample cell volume of ˜350 μL. Sample cell volumes areselectable. Thus, volumes are not limited. The present embodimentfurther eliminates plastic inserts within the volume of sample cell 3.Because plastic inserts are not employed within sample cell 3,background signals (e.g., ¹³C and ¹H background signals) aresignificantly suppressed, which represents a distinct advantage overconventional MAS rotors known in the art. In this embodiment, end plug 7and valve adapter 6 are not glued into rotor sleeve 1 in order tofacilitate filling, re-filling, and cleaning of sample cell 3, and toeffect rapid replacement of O-rings 9. In some embodiments, typical MASrotor 20 achieves sample spinning speeds of up to about 3.5 kHz. But,spinning speed is not intended to be limited. Maximum spinning speed islimited only by failure of the rotor sleeve, which is a function of thecentrifugal forces delivered to the rotor sleeve by both the samplespinning and the internal fluid pressure, as detailed further herein.MAS rotor 20 of the present invention achieves pressures exceeding thoseachieved with conventional rotors. In various embodiments, MAS rotor 20achieves sample pressures between about 70 bar and 150 bar. In someembodiments, MAS rotor 20 achieves fluid pressures (e.g., CO₂) of atleast about 100 bar. In yet other embodiments, MAS rotor 20 achievespressures exceeding 150 bar with minimal penetration pressure lossesover an extended period, as described further herein. No pressurelimitations are intended, 1 d shows a close-up view of high pressuresealing valve (end cap) 8. In the instant embodiment, sealing valve 8 isof a high-pressure fitting design that includes a conical (V-shaped)receiving end 10. Receiving end 10 exerts pressure on O-ring 9 throughadapter 6 positioned immediately adjacent the V-shaped end 10. Sealingin rotor sleeve 1 is achieved between sealing valve 8 and valve-adaptor6 when the tapered end of sealing valve 8 is threaded tightly into theconical shaped receiving end 10 of valve-adaptor 6. Sealing within therotor sleeve 1 is achieved by turning sealing valve. 8 less than half aturn. Consequently, pressure inside cell 3 after sealing is essentiallythe same as the outside pressure. Sealing valve 8 further includes anoff-center needle channel 12 located just off (˜1524 μm) the symmetricaxis of valve 8 that links to sample cell 3 when sealing valve 8 isloosened, allowing high-pressure fluids to be introduced into samplecell 3 prior to, or during an experiment; or, to release fluids fromsample cell 3 at any time during or after an experiment. Position anddimensions of needle channel 12 are not limited. Volume change of fluidsinside sample cell 3 before and after sealing is minimized, which isimportant for accurately setting up experimental conditions before thesample is moved to an NMR spectrometer or probe (not shown) foranalysis.

Centrifugal Force

The centrifugal force of a point mass, F_(c), due to spinning is givenby Equation [1], as follows:Fc=m*ω ² r=4π² *m*f ² *r  [1]

Here m is the mass (Kg); f is the rotating frequency (Hz); and r is thedistance (meters) between the rotating mass and the center of rotation.Pressure P_(c) is then given by:

$\begin{matrix}{P = \frac{Fc}{A}} & \lbrack 2\rbrack\end{matrix}$

Here A is the surface area. The centrifugal force F_(c) is converted toan equivalent pressure value P_(c), as given by Equation [3]:

$\begin{matrix}{P_{c} = {\frac{\frac{\Delta\;{\theta\left( {R_{2} + R_{1}} \right)}}{2}*\left( {R_{2} - R_{1}} \right)*L*\rho*\omega^{2}*R_{2}}{\Delta\;\theta*R_{1}*L} = \frac{\left( {R_{2} + R_{1}} \right)*\left( {R_{2} - R_{1}} \right)*\rho*\omega^{2}*R_{2}}{2*R_{1}}}} & \lbrack 3\rbrack\end{matrix}$

Here R₁ is the internal radius of the rotor sleeve; R₂ is the outerradius of the rotor sleeve; ρ is the density of the rotor sleeve (forzirconia, ρ=6.52 g/cm³); L is the length of the rotor sleeve (cylinder),and ω is the angle (in radians) of the very small arc spanned by thevery small mass. The equivalent pressure due to the centrifugal force isgiven by Equation [4] as follows:

$\begin{matrix}\begin{matrix}{P_{C} = \frac{\left( {R_{2} + R_{1}} \right)*\left( {R_{2} - R_{1}} \right)*\rho*\omega^{2}*R_{2}}{2*R_{1}}} \\{= {0.025405\frac{g}{mm}*4\;\pi^{2}f^{2}}} \\{= {1.002952\frac{g}{mm}f^{2}}} \\{= {1.002952\frac{kg}{m}f^{2}}} \\{= {\frac{1.002952}{100000}f^{2}{bar}}}\end{matrix} & \lbrack 4\rbrack\end{matrix}$

Here f is the sample spinning rate (units of Hz). At sample spinningrates of 2 kHz, 3.5 kHz, and 7 kHz, e.g., equivalent pressures due tospinning are 397 bar, 121.6 bar, and 486.6 bar, respectively. Rotorsleeve (cylinder) 1 is configured for high-pressure. MAS applications.In the exemplary embodiment, rotor sleeve 1 of rotor 20 is composed ofzirconia with dimensions that include an O.D. of 9.5 mm and an I.D. of 8mm. Rotor sleeve 1 can withstand a combined pressure from fluids andcentrifugal spinning forces up to 482 bar (7000 psi). For example, at asample spinning rate of 3.5 kHz (representing a centrifugal spinningforce of 121.6 bar), zirconia rotor sleeve 1 of the exemplary embodimentcan withstand a fluid pressure of about 360 bar (5400 psi) (i.e., 482bar minus 121.6 bar). Therefore, at operating pressures up to 150 barand above, rotor sleeve 1 is not a limiting factor for achieving amaximum fluid pressure in sample cell 3.

FIGS. 2 a-2 c show another embodiment of high-pressure MAS rotor 20, ofa 6.0 mm outer diameter (O.D.) design. In this embodiment, sealing valve8 inserts directly into bushing 5. In this embodiment, no valve adapter(FIG. 1 b) is employed within rotor sleeve 1 due to the narrow interiordiameter. All other assembly components are as previously described forFIGS. 1 a-1 d.

FIGS. 3 a-3 d show various alternate designs for the high-pressure MASrotor 20, according to different embodiments of the invention. In FIG. 3a, rotor 20 includes a rotor sleeve 1 that has one open end. In thisembodiment, a threaded bushing 5 is introduced through the upper end ofsleeve 1 and glued to sleeve 1 adjacent grooves machined into the wallalong sleeve 1, as described herein for FIG. 1. Sample cell 3 includesone closed end. Upper boundary of sample cell 3 is defined by positionof bushing 5 along sleeve 1. Sample cell 3 is sealed in concert with anO-ring 9 positioned atop bushing 5 and introduction of sealing valve 8.Drive tip 2 is a separate component that is inserted at the bottom ofrotor sleeve 1. In FIG. 3 b, rotor 20 includes a rotor sleeve 1 with oneopen end. In this embodiment, sleeve 1 includes threads machined intothe wall at the upper end of sleeve 1 into which sealing valve 8 isintroduced. Sample cell 3 includes one closed end. Sample cell 3 issealed by introducing sealing valve 8 through an O-ring 9 and screwingsealing valve 8 into threads along the wall at the upper end of sleeve1. Drive tip 2 is a separate component that is inserted at the bottom ofrotor sleeve 1. In FIG. 3 c, rotor 20 includes a rotor sleeve 1 that hasone open end. A threaded bushing 5 is introduced through the upper endof sleeve 1 and glued to sleeve 1 adjacent grooves machined into thewall along sleeve 1, as described herein for FIG. 1. Upper boundary ofsample cell 3 is defined by position of bushing 5 along sleeve 1. Samplecell 3 is sealed by introducing valve 8 through an O-ring 9 and turningsealing valve 8 into threads positioned along the interior wall ofbushing 5. In this embodiment, sealing valve 8 is of a combination drivetip/valve design in which the valve and drive tip are one body. Thisdesign permits rotation of rotor 20 from the top end of rotor 20. Inthis embodiment, a separate drive tip (FIG. 3 b) is not required. InFIG. 3 d, rotor 20 includes a rotor sleeve 1 with one open end. In thisembodiment, sleeve 1 includes threads machined into the wall at theupper end of sleeve 1 into which valve 8 is introduced. Sample cell 3 issealed by inserting sealing valve 8 through an O-ring 9 and turningsealing valve 8 into threads positioned along the inner wall at theupper end of sleeve 1. In this embodiment, sealing valve 8 is acombination valve and drive tip, which permits rotation of rotor 20 fromone end (e.g., the top end) of rotor 20. Thus, a separate drive tip(FIG. 3 b) is not required. A high-pressure rotor loading/reactorchamber will now be described.

High-Pressure MAS Rotor Loading Chamber/Reactor

FIGS. 4 a-4 e show different views of a high-pressure rotorloading/reaction chamber (HP-RLRC) 50, according to one embodiment ofthe invention. Loading chamber 50 is a high-pressure andhigh-temperature reaction device configured for both in situ sealing andin situ opening of the sealing valve (FIG. 1 and FIG. 2) of thehigh-pressure MAS rotor (HP-MAS-R). Loading chamber 50 includes a main(top) block portion 30 and a lower (bottom) block portion 32. Main (top)block portion 30 and lower (bottom) block portion 32 of high-pressureloading chamber 50, are constructed preferably of stainless steel. Inthe instant embodiment, main (top) block portion 30 and lower (bottom)block portion 32 are held together by eight bolts (e.g., 7.8 mm diameterand 120 mm long), but construction is not limited thereto. In thepresent embodiment, two O-rings 24 (e.g., two) composed of ahigh-performance elastomer are used to achieve a high-pressure sealbetween top block 30 and bottom block 32. High-performance elastomersinclude, but are not limited to, e.g., nitrile-containing elastomers(e.g., BUNA-90®, WARCO BILTRITE, Orange, Calif., USA), fluoroelastomers(e.g., VITON®, Dupont Performance Elastomers, LLC, Wilmington, Del.,USA) or other durable elastomers. In the present embodiment, the twoO-rings have typical dimensions of: 65 mm×2.5 mm OD×CS (cross-section ofthe O-ring diameter) and 50×2.5 mm OD×CS, respectively. Number ofO-rings is not limited. Top block portion 30 includes a rotationmechanism 25 (including a rotation shaft 22) and one or more viewingwindows 36 that facilitate engagement between rotating mechanism 25 andsealing valve 8 during sealing or reopening of the high-pressure MASrotor 20. Windows 36 are preferably made of a transparent material.Example window materials include, but are not limited to, e.g.,polycarbonate, quartz, and sapphire. In the instant embodiment, eachwindow 36 is held in place, e.g., with a stainless steel plate 37 andeight bolts, or another suitable construction. Loading chamber 50further includes a lower (bottom) portion 32 that includes rotor seat 48for holding the high-pressure MAS rotor 20 while the sample cell (FIG. 1and FIG. 2) is loaded with sample. In the present embodiment, athermocouple (not shown) is inserted into a channel 45 positioned nearor adjacent rotor seat 48 to measure temperature the level of thehigh-pressure MAS rotor 20.

Loading chamber 50 allows for loading and sealing of high-pressurefluids inside the high-pressure MAS rotor 20. In addition, loadingchamber 50 allows for repeated opening and sealing of valve 8 of thehigh-pressure MAS rotor 20 in-situ. Reactions can thus be carried outindefinitely under controlled high-pressure and temperature conditionsby returning the high-pressure MAS rotor 20 to the high-pressure rotorloading/reaction chamber 50, permitting introduction and re-introductionof high-pressure fluids, or an additional reagent or reactant intosample cell 3 of rotor 20. Operation of the rotation seal mechanism 25while loading the sample cell (FIGS. 1 and 2) is described hereafter.

FIG. 4 b shows a cut-away view of top block portion 30. In the figure,rotating (rotation) shaft 22 includes two O-rings 23, positioned, e.g.,to properly align, secure, and seal rotating shaft 22 within chamber 50.View windows 36 are positioned in top block portion 30 to view, andfacilitate engagement of, rotation mechanism 25 with sealing valve 8 ofthe high-pressure rotor 20 during operation. Upper block 30 furtherincludes one or more gas input ports 40 with control valves 42 thatallow several different gases to be introduced to chamber 50.

FIG. 4 c shows an exploded view of rotation mechanism 25 (in top portion30 of chamber 50) for sealing and opening of high-pressure MAS rotor 20in situ, and holding mechanism 26 (in bottom portion 32 of chamber 50)for mounting and tightly holding rotor 20 within chamber 50. In theinstant embodiment, when components are mounted in place, including thehigh-pressure MAS rotor 20, the net volume for the high-pressure fluidsin the reaction chamber is about 9 cm³. Upper block 30 includes one ormore input ports 40 with control valves 42 that allow several differentfluids to be introduced to chamber 50. Pressure gauges (not shown) mayalso be coupled to at least one fluid input port 40 to accurately readpressures inside the high-pressure loading chamber 50. Thermocouples(not shown) may be inserted through one or more fluid inlet ports 40 toaccurately measure temperature inside the high-pressure loading chamber50. Construction is not intended to be limited. All construction designsas will be implemented by those of ordinary skill in the art in view ofthe disclosure are within the scope of the invention.

FIG. 4 d shows a cross-sectional view of rotation mechanism 25 andholding mechanism 26 inside high-pressure MAS rotor 20. Rotation sealmechanism 25 includes a rotating (rotation) shaft 22 and a stainlesssteel high-pressure thrust bearing 24. Thrust bearing 24 facilitatesrotation of sealing valve 8 of rotor 20 under high-pressure. Rotatingshaft 22 includes a hexagonal shaped groove 18 positioned at one endthat engages the hexagonal head 16 of sealing valve 8, allowing fortightening and loosening of sealing valve 8. Cap plate 38 is securedatop top block portion 30 using, e.g., ten stainless screws, butconstruction is not limited thereto. Two O-rings 34 (e.g., a 60×2.5 mmO.D.×CS and a 40×2.5 mm OD×CS) positioned in grooves below cap plate 38atop top block portion 30 are used in combination with cap plate 38 toseal rotation mechanism 25 within chamber 50 at high-pressure. Cap plate38 also defines a center opening 39 through which one end of rotationshaft 22 extends after coupling to rotor 20. In bottom block portion 32,screw cap 44 defines a center opening 45 for insertion of rotor 20within chamber 50. Screw cap 44 includes an O-ring 46 positioned tosecure high-pressure rotor 20 in place. Screw cap 44, when attached,squeezes O-ring 46 tightly against the surface of rotor 20, securing andaligning high-pressure rotor 20 in place within chamber 50. Inoperation, friction is adequate to hold rotor 20 in place duringrotation of shaft 22.

FIG. 4 e presents an enlarged view of high-pressure rotor 20 showing theengagement between groove 18 of rotation shaft 22 and hexagonal head 16of sealing valve 8. As shown in the figure, rotation shaft 22 onlyundergoes rotational motion with no net vertical movement downward.Thus, in operation, only sealing valve 8 is driven vertically downwardwhile engaged with hexagonal groove 18 of rotation shaft 22 therebycreating the required seal. High-pressure chamber 50 is connected to aprimary programmable high-pressure syringe pump (e.g., a 100 cc ISCO-DSeries syringe pump, Teledyne Isco, Inc., Lincoln, Nebr., USA) rated toa pressure of, e.g., 500 bar, and a secondary piston screw pump (notshown) (e.g., a 10 cc, manually-operated piston screw pump,High-pressure Equipment Company, Erie, Pa., USA) that can boost pressureup to 4000 bar. A high-pressure bench (not shown) controls mixtures offluids introduced into high-pressure loading chamber 50 at selectedpressure and temperatures. Temperature of HP-RLRC 50 is controlled inconcert with a heating device (e.g., a 400° C. Cimarec® hotplate,ThermoFisher Scientific, Waltham, Mass., USA) that provides homogeneousheating of HP-RLRC 50.

Sample Loading

The following steps describe loading and sealing of samples andhigh-pressure gases in sample cell 3 of the 9.5 mm HP-MAS-R rotor 20design of FIG. 1. {START}. In a first step {202}, sample cell 3 iscleaned without end plug 7, valve-adaptor 6 and sealing valve 8components in place, Next {204}, sample is loaded into sample cell 3.Next {206}, after loading the sample, the inner thread of bushing 5 isoptionally cleaned of sample, and the valve-adaptor 6, including anyO-rings 9, are mounted in place. Next {208}, sealing valve 8 iscarefully mounted and turned into place. In some embodiments of theprocess, sealing valve 8 is immediately sealed upon mounting in caseswhere short exposure times with a selected fluid are desired. In otherembodiments of the process, sealing valve 8 is mounted and turned intoplace, but not sealed. In another step {210}, the assembled rotor 20with its assembled components is seated in rotor seat 48 in bottom blockportion 32 of the HP-RLRC 50 (see FIG. 2 d). Rotation shaft 22 alignswith, and engages, sealing valve 8 in high-pressure MAS rotor 20. Inanother step {210}, a desired fluid (or fluids) is introduced intosample cell 3 of the high-pressure rotor 20 at a selected fluid pressurethrough one or more fluid ports 40 of high-pressure loading chamber 50with the syringe pump assembly described previously herein. If sealingvalve 8 is not sealed during pressurization of HP-RLRC 50, then pressureinside and outside HP-MAS-R 20 is equal. If HP-RLRC 50 is pressurizedwith valve 8 sealed, needle channel 12 inside sealing valve 8 of thehigh-pressure MAS rotor 20 allows pressure outside and inside samplecell 3 to rapidly equalize when valve 8 is opened and fluid enterssample cell 3 of HP-MAS-R 20. After equilibrium pressure is attained,clockwise rotation of rotation shaft 22 seals the one or morehigh-pressure fluids inside MAS rotor 20. Likewise, a counter-clockwiserotation opens sealing valve 8 and exposes sample cell 3 through theneedle hole 12 in the sealing valve 8 to fluids present in high-pressurechamber 50. Opening and closing of sealing valve 8 when rotor 20 ismounted inside chamber 50 is preferably performed when pressure insideand outside the MAS rotor 20 are about the same to minimize the amountof external force or torque needed to perform the operation, but is notlimited thereto. {END}. As will be understood by those of ordinary skillin the art, method steps can be tailored for loading samples into thesample cell of other embodiments of the invention, Thus, no limitationsare intended.

Transferring High-Pressure Rotor

The pressurized HP-MAS-R 20 containing a preselected sample istransferred within a (e.g., a screw-capped) safety canister (not shown).In the instant embodiment, the safety canister is of a cylindrical shapedesign preferably composed of stainless steel which is preheated for aselected time (e.g., a few hours) at a selected temperature the sametemperature as in HP-RLRC 50) to maintain the rotor 20 at desiredtemperatures. Exemplary dimensions include 8 mm thick walls, a 16 mmthick bottom, and a top sealing cap. In-situ NMR is subsequently carriedout by sealing high-pressure MAS rotor (HP-MAS-R) 20 in high-pressureloading/reaction chamber (HP-RLRC) 50 in-situ and then moving the HP-MASrotor 20 with charged sample to the NMR spectrometer (not shown) formeasurements and analyses. In-situ NMR is thus representative ofreactions occurring at the same pressure and temperature conditionswithin HP-RLRC 50.

RF Coil with B1 Localization

FIG. 5 a shows an RF coil 60 of a saddle-coil design employed in concertwith the invention, according to an embodiment of the invention. The RFcoil 60 of the present embodiment includes 4 coil turns inclined at amagic angle of 54.74° with respect to the magnetic (bore) Z-axis. Insome embodiments, a magnetic field of 7.05 T is employed thatcorresponds to a ¹H Larmor frequency of 300 MHz. RF coil 60 delivers alocalized B₁ field that minimizes background NMR signals (¹³C and ¹Hbackground signals) stemming from plastic sealing components located atrespective ends of the high-pressure MAS rotor. In one embodiment, a ¹³C90 degree pulse is obtained using a 5.5 μs pulse width at an input powerof 504 Watts. Pulse and power selections are not intended to be limited.FIG. 5 b shows an RF Coil 60 according to another embodiment of theinvention. In the figure, RF Coil 60 includes two insulator panels 52for discharging charge and two RF shields 54 composed of thincylindrical copper plates positioned at respective ends of RF coil 60that improve B₁ localization in the sample cell (FIG. 1 and FIG. 2) ofthe high-pressure rotor. In some embodiments, RF shields 54 can be usedto minimize background signals in the NMR spectra arising from plasticsealing components employed within HP-MAS-R 20.

Background Signal Data

FIG. 6 a is a ¹³C single pulse MAS (i.e., SP-MAS) spectrum showingbackground signal data obtained while collecting measurements of naturalabundance supercritical CO₂ (scCO₂) with the 9.5 mm (O.D.) high-pressureMAS rotor at a pressure of 130 bar, a temperature of 50° C., and asample spinning rate of 1.7 kHz. The spectrum was acquired without ¹Hhigh power decoupling (HPDEC) to minimize contributions to thebackground signal stemming from plastic device components (e.g.,bushings) present in the high-pressure rotor. A total of 1600 scans(accumulations) and a recycle delay time of 1 second were employed. ALorentz line broadening of 40 Hz was applied before Fouriertransformation. Without line broadening, the linewidth of the ¹³C peakin the figure (located at about 126.0 ppm) is about 15.6 Hz. As shown inthe figure, minimal background signals were observed. And, a backgroundsignal peak (centered at about −2 ppm) arising from VITON® O-rings usedin the rotor has a low intensity as shown in the inset spectrum(expanded 32×) between −50 ppm and 50 ppm. FIG. 6 b is a ¹³C SP-MASspectrum showing background signal data obtained with the 9.5 mm (O.D.)high-pressure MAS rotor following release of pressurized CO₂ from thesample cell. Data were acquired at a temperature of 50° C., and a samplespinning rate of 1.7 kHz. In the figure, ¹H high power decoupling wasapplied to show actual background signal intensities arising fromindividual plastic device components (e.g., bushings, end plugs, valve,and valve adaptor) and/or CO₂ penetration in the high-pressure rotor(described previously in reference to FIGS. 1 and 2). Number of scans(accumulations) was 7200. A recycle delay of 2 seconds was used. Resultsshow low background signals (¹³C) are achieved by eliminating signalsarising from plastic components in the high pressure rotor in concertwith the RF Saddle coil (see FIG. 6 a). Further, background signals fromindividual components are weak despite a large number of scans. Thesedata further show that a good localization is achieved. Furthersuppression of the background signal can be achieved with improved RFlocalization, e.g., in concert with RF shields (see discussion FIG. 6 b)positioned at both ends of the RF Saddle Coil as described previouslyherein.

Gas Leakage at High Pressure

In exemplary tests, escape (i.e., leakage) of high pressure CO₂ from thehigh pressure rotor was measured over time. FIG. 7 a plots integrated¹³C peak intensity of supercritical CO₂ (scCO₂) at 50° C. (323 K) as afunction of holding time. Sample spinning rate was 1.64 kHz. InitialscCO₂ pressure in the sample rotor was 150 bar. Peak position of scCO₂is centered at 125.96 ppm. In the figure, signal decay is approximatelylinear with time. Results show about 81.4% of peak intensity remainseven after a holding time of 72 hours at 50° C. Integrated intensity ofthe CO₂ peak is directly proportional to the CO₂ density inside thefixed volume sample cell of the high-pressure rotor. Thus, density ofCO₂ as a function of holding time at temperature (e.g., 323 K) can bedetermined by multiplying percentage of CO₂ peak intensity remainingwith the initial CO₂ density (0.70 g/cm³). Results show a pressureexceeding 150 bar is achieved with minimal penetration loss of pressureover at least a period of 72 hours, FIG. 7 b plots expected CO₂densities calculated from in situ ¹³C MAS NMR measurement data in thesample cell of the high-pressure MAS rotor as a function of holdingtime. CO₂ density data were estimated by periodically weighing thehigh-pressure MAS rotor over a period of 27 hours. In the figure,density data are included for comparison with expected values obtainedfrom in situ measurements. Density data closely match the in situ ¹³CMAS experimental data, confirming their veracity. Given an initial CO₂density of 0.241304 g/cm³ at 83 bar and 323 K, if the integrated ¹³C NMRCO₂ peak intensity is greater than 79% of the initial integrated peakintensity, CO₂ inside the high-pressure MAS rotor remains supercritical.Chemical shift values for the CO₂ peak showed the peak center positionedat 125.96 ppm did not change over the same period. The stable peakposition confirms that the high-pressure MAS rotor is able to maintainCO₂ fluid above the supercritical point for at least 72 hours, startingfrom a pressure slightly above the critical point.

FIG. 8 shows in-situ ¹³C SP-MAS NMR spectra acquired with one embodimentof the invention obtained for the reaction between scCO₂ and anexemplary mineral, Forsterite (Mg₂SiO₄), as a function of reaction time.Data were acquired in-situ at a pressure of 150 bar and 50° C. over aperiod of 237 hours. Sample spin rate was 2.1 kHz. Number ofaccumulations (scans) was 26000 with a recycle delay of 2 seconds. TABLE1 lists reaction times for the experiment.

TABLE 1 Reaction times for in-situ experiment. Reaction Time insideHP-RLRC Re-Equilibration Acquisition Time Total Time (hours) (hours)^(a)(hours)^(b) (hours) 50 — 17 67 60 1.5 25 154 60 1.5 22 237^(a)Re-equilibration time represents a time window beginning from when aprevious NMR acquisition is stopped until the rotor valve is openedinside the HP-RLRC. In the present experiment, the valve was opened inthe HP-RLRC at a fluid pressure/temperature of 150 bar and 50° C., butis not limited. ^(b)Acquisition time represents the time needed tocollect ¹³C MAS NMR spectra in the NMR spectrometer.

At a reaction time of 67 hours, the figure shows a scCO₂ peak (centeredat 125.96 ppm) and a HCO₃ ⁻ peak (about 161 ppm). At a reaction time of53.5 hours, a third peak appears in the spectrum (centered at 170 ppm)corresponding to MgCO₃. At a reaction time of 237 hours, intensity ofthe MgCO₃ peak increases. These time series measurements show thatreaction intermediate species can be detected in-situ. For example, thepeak corresponding to HCO₃ ⁻ appears before the MgCO₃ peak is observed,indicating HCO₃ ⁻ to be a reaction intermediate in this reaction system.Further, HCO₃ ⁻ appears prior to any metal carbonate reaction products.Chemical shift values of HCO₃ ⁻ and H₂CO₃ are located at 161.2 ppm and162.9 ppm, respectively. With confidence the 161.52 ppm peak is assignedto HCO₃ ⁻.

After completing in-situ measurements (described previously in referenceto FIG. 8), ¹³C MAS spectra were acquired ex-situ on the previouslyreacted Forsterite (Mg₂SiO₄) sample following release of scCO₂ at roomtemperature and atmospheric pressure. Pressure in the sample cell wasreleased by opening the rotor valve (FIG. 1 and FIG. 2) and thenresealing the valve. FIG. 9 presents ¹³C MAS NMR spectra acquiredex-situ for the resulting mineral system as a function of time. Samplespin rate was 2.1 kHz. Number of scans was 165000 for the 61 dayspectrum, 192000 for the 63 day spectrum, and 220000 for the 65 dayspectrum, respectively. The first trace (time=0) was acquired followingcompletion of in-situ experiments immediately after releasing scCO₂. Inthe figure, sample contents include a mixture of newly formed MgCO₃ (asconfirmed by the MgCO₃ peak at 170 ppm) formed by reaction with CO₂during in-situ experiments and the remaining quantity of Forsterite(Mg₂SiO₄). Scans performed at 61 days, 63 days, and 65 days show theappearance and increase of hydration products such as magnesite,nesquehonite, and dypingite. Results show a metal carbonation reactionin a geological carbon sequestration related application. These datahighlight the value of a high pressure MAS capability, which allowsinvestigation of experimental conditions in various systems in-situ(“real conditions”) by MAS NMR.

While a number of embodiments of the present invention have been shownand described, it will be apparent to those skilled in the art that manychanges and modifications may be made without departing from theinvention in its broader aspects. The appended claims are thereforeintended to cover all such changes and modifications as fail within thescope of the invention.

What is claimed is:
 1. A high pressure loading and reaction device, theloading and reaction device comprising: a holding member for staticallymounting a high-pressure rotor therein, the high-pressure rotorincluding a high pressure rotor sleeve with a high-pressure sample celldefined therein; and a rotation member that engages and rotates asealing valve of the high-pressure sample cell within the rotor sleeve,providing sealing or opening of the sealing valve in-situ while thehigh-pressure rotor remains statically positioned in said device.
 2. Thehigh pressure loading and reaction device of claim 1, wherein therotation member is a high-pressure thrust bearing.
 3. The high pressureloading and reaction device of claim 1, further including at least onefluid port operatively coupled for introducing one or more fluidsindependently into the sample cell within the high pressure rotorin-situ.
 4. A method for sealing a high-pressure sample cell within ahigh-pressure rotor in-situ, comprising the steps of: introducing aquantity of sample within the high-pressure sample cell defined within ahigh-pressure rotor sleeve of said high-pressure rotor in-situpositioned within a high-pressure loading and reaction device, thehigh-pressure sample cell spans the entire inner diameter of the rotorsleeve of said high-pressure rotor; and sealing said sample within saidhigh-pressure sample cell of said high-pressure rotor positioned withinsaid high-pressure loading and reaction device at said pressure with ahigh-pressure sealing valve operatively coupled to said sample cell byturning same with a high-pressure thrust bearing, thereby sealing saidvalve.
 5. The method of claim 4, wherein sealing includes a pressurewithin the high-pressure sample cell greater than 1 bar.
 6. The methodof claim 4, wherein introducing the sample includes opening the sealingvalve of the high-pressure sample cell within the high-pressure rotorwithin said high-pressure loading and reaction device to rechargecontents within the sample cell in-situ.
 7. The method of claim 4,further including the step of analyzing said sample present within saidsample cell at said high pressure for a preselected time by introducingsaid high-pressure rotor containing said sample into an NMR probe.